Batteries are a useful source of stored energy that can be incorporated into a number of systems. Rechargeable lithium-ion batteries are attractive energy storage systems for portable electronics and electric and hybrid-electric vehicles because of their high specific energy compared to other electrochemical energy storage devices. In particular, batteries with a form of lithium metal incorporated into the negative electrode afford exceptionally high specific energy (in Wh/kg) and energy density (in Wh/L) compared to batteries with conventional carbonaceous negative electrodes.
When high-specific-capacity negative electrodes such as lithium are used in a battery, the maximum benefit of the capacity increase over conventional systems is realized when a high-capacity positive electrode active material is also used. Conventional lithium-intercalating oxides (e.g., LiCoO2, LiNi0.8Co0.15Al0.05O2, Li1.1Ni0.3Co0.3Mn0.3O2) are typically limited to a theoretical capacity of ˜280 mAh/g (based on the mass of the lithiated oxide) and a practical capacity of 180 to 250 mAh/g. In comparison, the specific capacity of lithium metal is about 3863 mAh/g. The highest theoretical capacity achievable for a lithium-ion positive electrode is 1168 mAh/g (based on the mass of the lithiated material), which is shared by Li2S and Li2O2. Other high-capacity materials including BiF3 (303 mAh/g, lithiated) and FeF3 (712 mAh/g, lithiated) are identified in Amatucci, G. G. and N. Pereira, Fluoride based electrode materials for advanced energy storage devices. Journal of Fluorine Chemistry, 2007. 128(4): p. 243-262. All of the foregoing materials, however, react with lithium at a lower voltage compared to conventional oxide positive electrodes, hence limiting the theoretical specific energy. The theoretical specific energies of the foregoing materials, however, are very high (>800 Wh/kg, compared to a maximum of ˜500 Wh/kg for a cell with lithium negative and conventional oxide positive electrodes).
Lithium/sulfur (Li/S) batteries are particularly attractive because of the balance between high specific energy (i.e., >350 Wh/kg has been demonstrated), rate capability, and cycle life (>50 cycles). Only lithium/air batteries have a higher theoretical specific energy. Lithium/air batteries, however, have very limited rechargeability and are still considered primary batteries.
While generally safe, the amount of energy stored within a battery as well as the materials used to manufacture the battery can present safety issues under different scenarios. Safety is particularly an issue when a battery is subjected to increased temperatures either as a result of internal processes or as a result of the environment in which the battery is located.
By way of example, when batteries are charged or discharged, they typically generate heat due to a finite internal resistance that includes ohmic, mass-transfer, and kinetic terms. Exothermic side reactions can also generate heat within the battery. This heat generation can pose a safety risk if it is large and rapid. For instance, commercial Li-ion cells generally go into thermal runaway if the internal cell temperature climbs above the decomposition temperature of the cathode (˜180 to 220° C., depending upon the chemistry and the state of charge). Often the events that lead to a temperature rise above this critical temperature are triggered at much lower temperatures. For example, exothermic anode film decomposition can occur at ˜120° C., providing enough energy to raise the battery temperature above 180° C. Excessive temperature in a battery may leading to venting of gases, smoke, flames, and, in rare cases, explosion.
Undesired amounts of heat may also be generated in a battery due to undesired physical changes in the battery. By way of example, formation of an electronically conducting phase between the two electrodes (i.e., internal shorting) of the battery can lead to excessive internal discharge. Internal shorting may be caused by dendrite formation, separator melting, separator cracking, separator tearing, pinholes, or growth of some conductive material through the separator.
In addition to safety concerns, increased temperatures impact the operational characteristics of the battery. At milder temperatures (40 to 100° C. for Li-ion batteries), aging of the battery is usually accelerated. This is due to the fact that most detrimental side reactions are thermally activated (although not all aging mechanisms in batteries are accelerated at high temperature). It is therefore advisable to cool batteries during operation and/or at high ambient temperatures in order to enhance their cycle and/or calendar life. There are numerous cooling concepts for commercial batteries, including active air cooling, liquid cooling, and the use of materials with high thermal conductivity.
External cooling of batteries, however, does not prevent localized areas of increased heat. For example, batteries that are placed in an ice bath and then heated internally during high current discharge could be maintained at the melting temperature of ice until the ice melts completely, but only at the external surface of the battery. Internally, the temperature of the battery at localized positions would be significantly higher, creating an uneven heat profile. The internal temperature of the battery could thus climb well above the melting temperature of ice.
What is needed therefore is a battery that is less susceptible to the deleterious effects of increased temperature. A further need exists for a battery that exhibits reduced internal self discharge when the separator function is compromised.